27 resultados para asymmetric allylation
Resumo:
This thesis investigates the effectiveness of time-varying hedging during the financial crisis of 2007 and the European Debt Crisis of 2010. In addition, the seven test economies are part of the European Monetary Union and these countries are in different economical states. Time-varying hedge ratio was constructed using conditional variances and correlations, which were created by using multivariate GARCH models. Here we have used three different underlying portfolios: national equity markets, government bond markets and the combination of these two. These underlying portfolios were hedged by using credit default swaps. Empirical part includes the in-sample and out-of-sample analysis, which are constructed by using constant and dynamic models. Moreover, almost in every case dynamic models outperform the constant ones in the determination of the hedge ratio. We could not find any statistically significant evidence to support the use of asymmetric dynamic conditional correlation model. In addition, our findings are in line with prior literature and support the use of time-varying hedge ratio. Finally, we found that in some cases credit default swaps are not suitable instruments for hedging and they act more as a speculative instrument.
Resumo:
Preparation of optically active compounds is of high importance in modern medicinal chemistry. Despite recent advances in the field of asymmetric synthesis, resolution of racemates still remains the most utilized way for preparation of single enantiomers in industrial scale due to its cost-efficiency and simplicity. Enzymatic kinetic resolution (KR) of racemates is a classical method for separation of enantiomers. One of its drawbacks is the limitation of target enantiomer yield to 50%. Dynamic Kinetic Resolution (DKR) allows to reach yields up to 100% by in situ racemization of the less reactive enantiomer. In the first part of this thesis, a number of half-sandwich ruthenium complexes were prepared and evaluated as catalysts for racemization of optically active secondary alcohols. A leading catalyst, Bn5CpRu(CO)2Cl, was identified. The catalyst discovered was extensively characterized by its application for DKR of a broad range of secondary alcohols in a wide range of reaction loadings (1 mmol – 1 mol). Cost-efficient chromatography-free procedure for preparation of this catalyst was developed. Further, detailed kinetic and mechanistic studies of the racemization reactions were performed. Comparison of racemization rates in the presence of Bn5CpRu(CO)2Cl and Ph5CpRu(CO)2Cl catalysts reveals that the performance of the catalytic system can be adjusted by matching of the electronic properties of the catalysts and the substrates. Moreover, dependence of the rate-limiting step from the electronic properties of the reagents was observed. Important conclusions about reaction mechanism were made. Finally, an alternative approach to DKR of amines based on space separated vessels was addressed. This procedure allows the combination of thermolabile enzyme with racemization catalysts active only at high temperatures.
Resumo:
Tässä tutkimuksessa oli tavoitteena tarkastella analyyttisen laskennan keinoin pienahitsin mitoittamista ja selvittää käytännön kokeissa havaittu a-mitasta poikkeavan vauriotason sijainti poikittain kuormitetuissa pienahitseissä. Perinteinen laskentamallin tarkastelu laa-jennettiin koskemaan mielivaltaisessa kulmassa olevaa laskentatasoa ja suurimman yhdistetyn jännityksen perusteella löydettiin kriittisin leikkaus tasakylkisessä hitsissä. Lisäksi tarkasteltiin voimatasapainon huomioon ottamista mitoituksessa ja luotiin kaksi eri mallia tämän pohjalta. Kolme teoreettisesti oikeampaa mitoitusmallia täydennettiin kattamaan myös erikylkiset hitsit ja todettiin, että kaikilla mitoitusmalleilla erikylkiset hitsit ovat tilavuudeltaan optimaalisempia verrattaessa samanlujuisiin tasakylkisiin hitseihin.
Resumo:
Tutkielmassa käsitellään markkina- ja sääntelyhäiriötä ja keskitytään selittämään, millä tavoin nämä häiriöt aiheuttavat taloudellista tehottomuutta. Lisäksi työssä osoitetaan markkina- ja sääntelyhäiriöiden välinen yhteys ja selitetään, kuinka markkina- ja sääntelyhäiriöiden ilmenemistä voitaisiin vähentää.
Resumo:
Työssä tutkittiin Ruukki Oyj:n suorasammutetusta S960QC-teräksestä valmistetun kuormaakantavan levyjen ristiliitoksen pienahitsien lujuutta, muodonmuutoskykyä ja vaurioitumismekanismia laajaan kokeelliseen aineistoon perustuen. Tärkeimpänä muuttujana koematriisissa olivat eri MAG-hitsausprosessit. Perinteisen kuumakaarihitsauksen vertailukohteena oli Kemppi Oy:n uusi adaptiivinen valokaaren pituutta säätävä WiseFusion-hitsaustoiminto kuuma- ja pulssikaarihitsauksessa. Näiden kolmen hitsausprosessin rinnalla varioitiin erisuuruisia a-mittoja, eri hitsauslisäaineita ja hitsin erikylkisyyttä. Lisäksi juuritunkeuman estämisen vaikutusta hitsien käyttäytymiseen tutkittiin täydentävällä koesarjalla, jossa tunkeuman muodostuminen estettiin levyjen väliin asetetulla volframilevyllä. Työn perimmäisenä tavoitteena oli selvittää syy aiemmassa tutkimuksessa havaitulle pienahitsien vaurioitumiselle leikkautumalla sularajaa pitkin. Sularajan suhteellista pituutta saadaan kasvatettua estämällä hitsin juuritunkeuma ja absoluuttista pituutta saadaan lisää kateettipoikkeaman avulla. Lisäksi tutkimuksessa oli tarkoitus tuoda esille suurlujuusteräksisen liitoksen eri mitoituslähtökohdat (mm. lämmöntuonnin kontrollointi). Tämän vuoksi hitsausparametrit mitattiin jännitteen ja virran hetkellisiin arvoihin perustuen, jolloin kuuma- ja pulssikaarihitsauksen laskennalliset hitsaustehot ovat vertailukelpoisia. Koehitseistä valmistettiin hieet hitsien tarkan geometrian määrittämiseksi ja liitoksen mekaaniset ominaisuudet tutkittiin vetokokeella. Tulosten perusteella sularajavaurio aktivoituu pulssikaarella hitsatuissa koekappaleissa. Tämä aiheutunee pulssi- ja kuumakaarihitsauksen sularajan mikrorakenteiden eroavaisuudesta. Sularajavaurio näyttää huonontavan hitsien muodonmuutoskykyä, mutta jatkokokeita tuloksen verifioimiseksi on tehtävä. S960QC-teräkselle ominaisen pehmenneen vyöhykkeen vaurio ei aktivoitunut, vaikka Ruukin antamat jäähtymisaikasuositukset ylitettiin reilusti.
Resumo:
Biorefining is defined as sustainable conversion of biomass into marketable products and energy. Forests cover almost one third of earth’s land area, and account for approximately 40% of the total annual biomass production. In forest biorefining, the wood components are, in addition to the traditional paper and board products, converted into chemicals and biofuels. The major components in wood are cellulose, hemicelluloses, and lignin. The main hemicellulose in softwoods, which are of interest especially for the Nordic forest industry, is O-acetyl galactoglucomannan (GGM). GGM can be isolated in industrial scale from the waste waters of the mechanical pulping process, but is not yet today industrially utilized. In order to attain desired properties of GGM for specific end-uses, chemical and enzymatic modifications can be performed. Regioselective modifications of GGM, and other galactose-containing polysaccharides were done by oxidations, and by combining oxidations with subsequent derivatizations of the formed carbonyl or carboxyl groups. Two different pathways were investigated: activation of the C-6 positions in different sugar units by TEMPO-mediated oxidation, and activation of C-6 position in only galactose-units by oxidation catalyzed by the enzyme galactose oxidase. The activated sites were further selectively derivatized; TEMPO-oxidized GGM by a carbodiimide-mediated reaction forming amides, and GO-oxidized GGM by indium-mediated allylation introducing double or triple bonds to the molecule. In order to better understand the reaction, and to develop a MALDI-TOF-MS method for characterization of regioselectively allylated GGM, α-D-galactopyranoside and raffinose were used as model compounds. All reactions were done in aqueous media. To investigate the applicability of the modified polysaccharides for, e.g., cellulose surface functionalization, their sorption onto pulp fibres was studied. Carboxylation affects the sorption tendency significantly; a higher degree of oxidation leads to lower sorption. By controlling the degree of oxidation of the polysaccharides and the ionic strength of the sorption media, high degrees of sorption of carboxylated polysaccharides onto cellulose could, however, be obtained. Anionic polysaccharides were used as templates during laccase-catalyzed polymerization of aniline, offering a green, chemo-enzymatic route for synthesis of conducting polyaniline (PANI) composite materials. Different polysaccharide templates, such as, native GGM, TEMPO-oxidized GGM, naturally anionic κ-carrageenan, and nanofibrillated cellulose produced by TEMPO-oxidation, were assessed. The conductivity of the synthesized polysaccharide/PANI biocomposites varies depending on the polysaccharide template; κ-CGN, the anionic polysaccharide with the lowest pKa value, produces the polysaccharide/PANI biocomposites with the highest conductivity. The presented derivatization, sorption, and polymerization procedures open new application windows for polysaccharides, such as spruce GGM. The modified polysaccharides and the conducting biocomposites produced provide potential applications in biosensors, electronic devices, and tissue engineering.
Resumo:
Työssä selvitettiin uuden kostutuslaitteen toimivuutta kartongin käyristymisen hallinnassa. Työn tavoitteena oli löytää kostutuslaitteelle energiatehokas ja käyttäjäystävällinen ajotapa. Lisäksi pyrittiin etsimään tärkeimmät kartongin käyristymiseen vaikuttavat prosessimuuttujat ja selvittämään voidaanko niitä hyödyntää käyryyden hallinnassa. Työssä tutkittiin myös kostutuslaitteen käytön vaikutuksia kartongin muihin tärkeisiin ominaisuuksiin, jotta saataisiin selville miten uusi tuote eroaisi referenssituotteesta. Kirjallisuusosassa selvitetään, mitkä tekijät vaikuttavat kartongin käyristymiseen ja miten käyristymistä pystytään hallitsemaan. Kirjallisuusosassa käsitellään myös, miten kartongin käyristymiseen tarvittavat epäsymmetriset mittamuutokset kartongin rakenteessa syntyvät lähtien kosteuden vaikutuksista aina yksittäisten kuitujen tasolta koko kartongin rakenteeseen asti. Kokeellisessa osassa selvitetään Inkeroisten Kartonkitehtaan kartonkikoneella ajettujen koeajojen avulla toimivaa ajotapaa kostutuslaitteelle ja eri prosessimuuttujien vaikutusta käyristymiseen. Koeajoissa tutkittiin epäsymmetrisen kostutuksen, kuivatuksen, sitoutuneisuuden, sekä kuituorientaation vaikutuksia kartongin käyristymiseen. Koeajojen perusteella merkittävimmiksi tekijöiksi kartongin käyristymiseen osoittautuivat epäsymmetrinen kostutus sekä kuivatus. Muiden tekijöiden vaikutus kartongin käyristymiseen jäi vähäiseksi tai liian epäselväksi, jotta olisi voitu osoittaa, että muutos kartongin käyryydessä johtuisi nimenomaan kyseisen tekijän muutoksesta. Verrattaessa uutta tuotetta referenssituotteeseen kartongin pinta- tai lujuusominaisuuksissa ei havaittu tapahtuvan merkittävää muutosta, kun selkäkerroksen pintaliimaus korvattiin sumukostutuksella.
Resumo:
Asymmetric synthesis using modified heterogeneous catalysts has gained lots of interest in the production of optically pure chemicals, such as pharmaceuticals, nutraceuticals, fragrances and agrochemicals. Heterogeneous modified catalysts capable of inducing high enantioselectivities are preferred in industrial scale due to their superior separation and handling properties. The topic has been intensively investigated both in industry and academia. The enantioselective hydrogenation of ethyl benzoylformate (EBF) to (R)-ethyl mandelate over (-)-cinchonidine (CD)-modified Pt/Al2O3 catalyst in a laboratory-scale semi-batch reactor was studied as a function of modifier concentration, reaction temperature, stirring rate and catalyst particle size. The main product was always (R)-ethyl mandelate while small amounts of (S)-ethyl mandelate were obtained as by product. The kinetic results showed higher enantioselectivity and lower initial rates approaching asymptotically to a constant value as the amount of modifier was increased. Additionally, catalyst deactivation due to presence of impurities in the feed was prominent in some cases; therefore activated carbon was used as a cleaning agent of the raw material to remove impurities prior to catalyst addition. Detailed characterizations methods (SEM, EDX, TPR, BET, chemisorption, particle size distribution) of the catalysts were carried out. Solvent effects were also studied in the semi-batch reactor. Solvents with dielectric constant (e) between 2 and 25 were applied. The enantiomeric excess (ee) increased with an increase of the dielectric coefficient up to a maximum followed by a nonlinear decrease. A kinetic model was proposed for the enantioselectivity dependence on the dielectric constant based on the Kirkwood treatment. The non-linear dependence of ee on (e) successfully described the variation of ee in different solvents. Systematic kinetic experiments were carried out in the semi-batch reactor. Toluene was used as a solvent. Based on these results, a kinetic model based on the assumption of different number of sites was developed. Density functional theory calculations were applied to study the energetics of the EBF adsorption on pure Pt(1 1 1). The hydrogenation rate constants were determined along with the adsorption parameters by non-linear regression analysis. A comparison between the model and the experimental data revealed a very good correspondence. Transient experiments in a fixed-bed reactor were also carried out in this work. The results demonstrated that continuous enantioselective hydrogenation of EBF in hexane/2-propanol 90/10 (v/v) is possible and that continuous feeding of (-)-cinchonidine is needed to maintain a high steady-state enantioselectivity. The catalyst showed a good stability and high enantioselectivity was achieved in the fixed-bed reactor. Chromatographic separation of (R)- and (S)-ethyl mandelate originating from the continuous reactor was investigated. A commercial column filled with a chiral resin was chosen as a perspective preparative-scale adsorbent. Since the adsorption equilibrium isotherms were linear within the entire investigated range of concentrations, they were determined by pulse experiments for the isomers present in a post-reaction mixture. Breakthrough curves were measured and described successfully by the dispersive plug flow model with a linear driving force approximation. The focus of this research project was the development of a new integrated production concept of optically active chemicals by combining heterogeneous catalysis and chromatographic separation technology. The proposed work is fundamental research in advanced process technology aiming to improve efficiency and enable clean and environmentally benign production of enantiomeric pure chemicals.
Resumo:
This thesis estimates long-run time variant conditional correlation between stock and bond returns of CIVETS (Colombia, Indonesia, Vietnam, Egypt, Turkey, and South Africa) nations. Further, aims to analyse the presence of asymmetric volatility effect in both asset returns, as well as, obverses increment or decrement in conditional correlation during pre-crisis and crisis period, which lead to make a reliable diversification decision. The Constant Conditional Correlation (CCC) GARCH model of Bollerslev (1990), the Dynamic Conditional Correlation (DCC) GARCH model (Engle 2002), and the Asymmetric Dynamic Conditional Correlation (ADCC) GARCH model of Cappiello, Engle, and Sheppard (2006) were implemented in the study. The analyses present strong evidence of time-varying conditional correlation in CIVETS markets, excluding Vietnam, during 2005-2013. In addition, negative innovation effects were found in both conditional variance and correlation of the asset returns. The results of this study recommend investors to include financial assets from these markets in portfolios, in order to obtain better stock-bond diversification benefits, especially during high volatility periods.
Resumo:
Nelivalssaimia käytetään yleisesti metallinauhojen ja -levyjen kylmämuovaukseen. Valssaimissa ristinivel siirtää vääntömomenttia kahden kulmassa olevan akselin välillä. Tässä tutkimuksessa haettiin ratkaisuja nelivalssaimessa esiintyvään epäsymmetriseen taivutustarpeeseen. Valssattavat kuparinauhat alkavat aaltoilla valssaajan puolelta noin yhden millimetrin paksuudessa. Tutkimuksen tarkastelu rajattiin koskemaan vain voimansiirrossa olevaa ristiniveltä, jonka epäiltiin olevan yksi mahdollinen ongelman aiheuttaja. Tutkimuksessa selvisi, että ristinivel ei aiheuta pystysuuntaisia voimia, jotka vaikuttaisivat suoraan nauhan poikkipintaprofiiliin. Kuitenkin ristinivelen aiheuttamat vaakasuuntaiset voimat voivat vaikuttaa epäsuorasti nauhan poikkipintaprofiiliin. Laatupoikkeamien taloudellinen merkitys havaittiin pieneksi, mutta myöhemmissä prosessivaiheissa kuparinauhan epäsymmetrinen poikkipintaprofiili aiheutti ongelmia.
Resumo:
This master’s thesis was made in order to gain answers to the question of how the integration of the marketing communications and the decision making related to it in a geographically dispersed service organization could be improved in a situation where an organization has gone through a merger. The effects of the organizational design dimensions towards the integration of the marketing communications and the decision making related to it was the main focus. A case study as a research strategy offered a perfect frames for an exploratory study and the data collection was conducted by semi-structured interviews and observing. The main finding proved that from the chosen design dimensions, decentralization, coordination and power, could be found specific factors that in a geographically dispersed organization are affecting the integration of the marketing communications negatively. The effects can be seen mostly in the decision making processes, roles and in the division of responsibility, which are affecting the other dimensions and by this, the integration. In a post-merger situation, the coordination dimension and especially the information asymmetry and the information flow seem to have a largest affect towards the integration of the marketing communications. An asymmetric information distribution with the lack of business and marketing education resulted in low self-assurance and at the end in fragmented management and to the inability to set targets and make independent decisions. As conclusions it can be stated, that with the organizational design dimensions can the effects of a merger towards the integration process of the marketing communications to be evaluated.
Resumo:
In the last few decades, banking has strongly internationalized and become more complex. Hence, bank supervision and regulation has taken global perspective, too. The most important international regulation are the Basel frameworks by the Basel committee on banking supervision. This study examines the effects of bank supervision and regulation, especially the Basel II, on bank risk and risk-taking. In order to separate and recognize the efficiency of these effects, the co-effects of many supervisory and regulatory tools together with other relevant factors must be taken into account. The focus of the study is on the effects of asymmetric information and banking procyclicality on the efficiency of the Basel II. This study tries to find an answer, if the Basel II, implemented in 2008, has decreased bank risk in banks of European Union member states. This study examines empirically, if the volatility on bank stock returns have changed after the implementation of the Basel II. Panel data consists of 62 bank stock returns, bank-specific variables, economic variables and variables concerning regulatory environment between 2003 and 2011. Fixed effects regression is used for panel data analysis. Results indicate that volatility on bank stock returns has increased after 2008 and the implementation of the Basel II. Result is statistically very significant and robustness has been verified in different model specifications. The result of this study contradicts with the goal of the Basel II about banking system stability. Banking procyclicality and wrong incentives for regulatory arbitrage under asymmetric information explained in theoretical part may explain this result. On the other hand, simultaneously with the implementation of the Basel II, the global financial crisis emerged and caused severe losses in banks and increased stock volatility. However, it is clear that supervision and regulation was unable to prevent the global financial crisis. After the financial crisis, supervision and regulation have been reformed globally. The main problems of the Basel II, examined in the theoretical part, have been recognized in order to prevent problems of procyclicality and wrong incentives in the future.